Dyeing keratin fibers with 2-substituted m-toluenediamines

ABSTRACT

Oxidation dye compositions particularly useful for dyeing human hair containing as the meta component compounds of the formula: ##STR1## or their non-toxic salts, wherein R is alkyl, hydroxyalkyl, phenylalkyl, phenylsulfonyls, alkylsulfonyls or cyanoalkyl.

This is a division, of application Ser. No. 406,442, filed 10/15/73 nowabandoned.

This invention relates to compositions and methods for dyeing keratinfibers using certain 2-substituted m-toluenediamines and to certainnovel compounds of this class. More particularly, it concernscompositions and methods for dyeing human hair, either in the form of awig or as natural hair on the human head, which employ 2-substitutedm-toluenediamines of the formula: ##STR2## or their non-toxic salts(e.g. HCl, HBr, H₂ SO₄, acetate, etc. salts), wherein R is alkyl,hydroxyalkyl, phenylalkyl, phenylsulfonyls, alkylsulfonyls (e.g. CH₃ SO₂--) and cyanoalkyl (e.g. --CH₂ CN).

It is known that in the present state of the hair dye art that only theso-called oxidation dyes give permanent dyeing in all shades.Practically all permanent dyes are formulated as oxidation dyecompositions which give a large variety of shades, especially thenatural ones. These dye compositions are formulated as mixtures of paracomponents as, for example, aromatic diamines, aminophenols or phenols;and meta components as, for example, m-toluenediamine,m-phenylenediamine. The mixture of para and meta components reacts onthe hair in the presence of hydrogen peroxide to form colors.

The shades obtained with these dye compositions are permanent andresistant to shampooings. However, the dyeings are not entirelysatisfactory because the darker shades, especially the blue componentsof these shades, have a tendency to go redder with time. This reddeningis accentuated by perspiration and sunlight. After a month, for example,the hair shows an unpleasant reddish cast.

It has now been found that when substituted m-toluenediamines of FormulaI above are used as meta components in oxidation dye compositions, dyeshades are obtained on hair that are fast to perspiration and light andwhich do not undergo a further oxidation toward reddish hues. The shadesobtained are also more resistant to repeated shampooings (i.e. washfast)with considerably less change in color than with m-toluenediamine. Theyalso give a better coverage, i.e. the dyeings exhibit the same intensityof color with less dye than, for example, 2,4-diaminoanisol, anothermeta component used in hair dyes.

It is accordingly an object of the present invention to provide dyecompositions and particularly hair dye compositions of the permanenttype which when dyed on hair are more resistant to off color wearing;are more wash fast, light fast and perspiration fast than prior artcompositions of this character.

It is also an object of the present invention to provide hair dyecompositions of the aforesaid type and having the aforesaid propertieswhich employ as the meta component in oxidation dye compositions acompound of Formula I above.

It is a further object of this invention to provide methods for dyeingkeratin fibers and particularly human hair which employs the aforesaidhair dye compositions.

Other and more detailed objects of this invention will be apparent fromthe following description and claims.

In the 2-substituted m-toluenediamine described above in Formula I thechain length of the alkyl chain or alkyl moiety of the compound radicals(e.g. hydroxyalkyl, phenylalkyl) may vary. Ordinarily, the alkyl chainor alkyl moiety will be of the lower chain length variety containing 1to 6 carbon atoms. When R is a hydroxyalkyl radical it will ordinarilycontain from 1 to 3 hydroxy groups.

To further illustrate more specifically the various values that R mayhave in Formula I the following are given:

(1) R = alkyl; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,ter-butyl, pentyl, hexyl.

(2) R = hydroxyalkyl: (preferably 2 to 6 carbon atoms and 1 to 3 hydroxygroups); hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl;2,3-dihydroxypropyl, 4-hydroxybutyl; 1,3-dihydroxypropyl,4-hydroxybutyl; 1,3-dihydroxypropyl, tris(hydroxymethyl)methyl.

(3) R = phenylalkyl; benzyl, phenylethyl, phenylpropyl, ##STR3## (4) R =alkylsulfonyl or phenylsulfonyls: methylsulfonyl (CH₃ --SO₂ --);ethylsulfonyl (C₂ H₅ --SO₂ --); propylsulfonyl (CH₃ --CH--CH₂ SO₂ --),##STR4## (5) R = cyanoalkyls: cyanomethyl (--CH₂ --CN); cyanoethyl(--CH₂ --CH₂ --CH); cyanopropyl (--CH₂ --CH₂ --CH₂ CN); cyanobutyl(--CH₂ (CH₂)₃ CN).

Among the above groups of compounds it has been found that the bestresults are obtained with those compounds in which R is alkyl orhydroxyalkyl. These, accordingly, form a preferred group of metacomponents which can be advantageously used in oxidation dyecompositions in accordance with the present invention.

The 2-substituted m-toluenediamines employed in the present inventionmay be readily prepared using reactions that are well known in the priorart. The reaction of choice will depend upon the particular substituentthat is introduced into the amine nitrogen. Below are given some of thetypical reactions for preparing these compounds: ##STR5## wherein:

X = halogen

Y = H, OH, CN

R = the divalent radicals; alkylene (e.g. --CH₂ --CH₂ --),phenylalkylene ##STR6## wherein R is a divalent alkylene orhydroxyalkylene group. ##STR7## wherein R = alkyl, phenyl orphenylalkyl.

The dyes described above in Formula I are intended for use mainly asmeta components in oxidation dye compositions. These are usually aqueousalkaline compositions that contain, in addition to the meta component,at least one para component. Optionally, such composition may alsocontain such things as modifier dye intermediates, nitro dyes, soaps,surfactants, thickening agents, antioxidants and organic solvents.Furthermore, these aqueous compositions may take various forms such assolutions, flowable liquids, pastes, creams or gels.

Illustrations of the para components that may be used in this inventionmention may be made of the following: p-toluenediamine, p-aminophenol,p-aminodiphenylamine, 4,4'-diaminodiphenylamine, p-phenylenediamine,2,6-dimethyl-p-phenylenediamine, 2,5-diaminopyridine. Of specialinterest is a class of para components described by the formula:##STR8## or its non-toxic salts, in which:

R₁ is alkyl or hydroxyalkyl;

R₂ is hydrogen or hydroxyalkyl;

R₃ is hydrogen, alkyl, alkoxy or halogen; and

R₄ occupies any one of the remaining positions on the benzene radicaland is hydrogen, alkyl, alkoxy or halogen; providing that R₂ is hydrogenwhen R₃ is alkyl, alkoxy or halogen and providing that at least two ofR₁, R₂, R₃ or R₄ are other than hydrogen. In this case too the alkylgroups or alkyl moieties contain 1 to 6 carbon atoms and thehydroxyalkyl contains from 1 to 3 hydroxy groups. The halogen may be Cl,Br, Fl, I, etc.

In addition to the meta and para components, the oxidation dyecompositions of this invention may contain other modifier dyeintermediates. These include such things as the m-aminophenols,compounds containing active methylene groups, phenols, etc.m-Aminophenols can give either indophenols or indamines on oxidativecoupling with para components. The products are usually violet in colorand are used in modifying shades. Examples of aminophenols useful hereinare 2,4-diaminophenol, m-aminophenol, aminoresorcinol,1,5-aminohydroxynaphthalene and 1,8-aminohydroxynaphthalene.

Compounds containing active methylene groups are also capable ofreacting with the oxidatively activated para components. The productsare imino compounds of various types and are yellow or red in color.Examples of active methylene compounds employable in the presentinvention are 3-methylpyrazolone-(5), 1-phenyl-3-methylpyrazolone-(5);1,3-dimethylpyrazolone-(5), acetoacetic acid anilide,benzoylacetotoluide and nicotinoylacetanilide.

Still other oxidation dye intermediates, i.e. modifiers, may be presentin the compositions of this invention which produce colored productsunder oxidative conditions by more complex mechanisms. This may includeone or more of self-coupling, or coupling with the para components orwith other intermediates present. Among these may be mentionedhydroquinone, catechol, 1,5-naphthalenediol, o-phenylenediamine,o-aminophenol.

Phenols react with para components, in the presence of oxidizing agents,to produce indophenols. These are usually blue or violet compounds,although resorcinols give yellow or brown colored compounds under theseconditions. The brown colors obtained from the reaction of resorcinolsare commonly used to produce the depth of a shade. Examples of phenolsuseful in oxidation dye compositions of this invention are pyrogallol,resorcinol, pyrocatechol and alphanaphthol.

It is sometimes desirable to add to said oxidation dye mixture dyeswhich are already colored i.e. which do not require an oxidizing agentfor color development. These are generally added for blending purposesto obtain natural looking colors in the final dyeing operation. Oneclass of dyes which may be used for this purpose is the nitro dyes andthis component is generally referred to herein as the nitro dyecomponent. A larger number of nitro dyes are known in the prior artwhich are suitable for this purpose. The only limitation that is placedon a nitro dye to be useful in the present invention is that it be onewhose color is not destroyed by the oxidizing agent used in the finalcolor development of the oxidizable components. By way of illustratingsuitable nitro dyes, mention may be made of the following:4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine,4-nitro-2-aminophenol, 5-nitro-2-aminophenol, 2-nitro-4-aminophenol andpicramic acid.

The pH of the oxidation dye mixture of this invention will generally beon the basic side e.g. 8-11. It is preferred, however, that this pH bein the range of about 9-10.

Any of a wide variety of alkalizing agents can be used to adjust the pHof the dyeing composition on the basic side. Ammonium hydroxide, becauseof its freedom from toxicity over a wide concentration range and itseconomy, is an acceptable alkalizing agent. However, there can be usedin place of, or together with, ammonia any other compatible ammoniaderivative as an alkalizing agent, such as an alkylamine, such asethylamine, or triethylamine; or alkanolamine, such as monoethanolamineor diethanolamine. Likewise, any other of the common alkalizing agentsmay be used, such as sodium or potassium hydroxide, sodium or potassiumcarbonate, sodium phosphate, sodium hydrogen phosphate, sodium silicate,and the like.

Among the soaps which may be present in the compositions of thisinvention may be mentioned the sodium, ammonium or potassium salts oflauric, stearic, palmitic, oleic, linoleic or ricinoleic acid. The soapsmay be present to the extent of 5-35% of the weight of the oxidation dyemixture, and preferably 15-25%.

Among the surface active agents useful in the present invention, mentionmay be made of the water-soluble surface active agents. These can beanionic, non-ionic or cationic. Illustrative of the various types ofwater-soluble surface active agents there can be mentioned: higheralkylbenzenesulfonates; alkylnaphthalenesulfonates; sulfonated esters ofalcohols and polybasic acids; taurates; fatty alcohol sulfates; sulfatesor branched chain or secondary alcohols; alkyl dimethylbenzyl ammoniumchlorides; and the like. Illustrative of specific surfactants there canbe mentioned: sodium lauryl sulfate; polyoxyethylene lauryl ester;myristyl sulfate; glyeryl monostearate; sodium salt of palmitic methyltaurine; cetyl pyridinium chloride; lauric diethanolamide;polyoxyethylene stearate; stearyl dimethyl benzyl ammonium chloride;dodecyl benzene sodium sulfonate; nonyl naphthalene sodium sulfonate;dioctyl sodium sulfosuccinate; sodium N-methyl-N-oleoyl taurate; oleicacid ester of sodium isothionate; sodium dodecyl sulfate; the sodiumsalt of 3,9-diethyl-tridecanol-6-sulfate and the like. The quantity ofwater-soluble surface active agent when present can vary over a widerange, such as that of from about 0.5% to 30% by weight of thecomposition, and preferably 1-10%.

Various organic solvents may also be present in the oxidation dyemixture for the purpose of solubilizing a dye intermediate or any othercomponent which may be insufficiently soluble in water. Generally, thesolvent selected is such as to be miscible with water and innocous tothe skin, and includes for example, ethanol, isopropanol, glycerine,ethylene glycol, propylene glycol, ethylene glycol monoethyl ether,diethylene glycol, diethylene glycol monoethyl ether, etc. The amount ofsolvent used may vary from 1-40% of the oxidation dye mixture, andpreferably 5-30%.

To exemplify the thickening agents that can also be incorporated in thepresent dyeing composition, mention may be made of sodium alginate orgum arabic, or cellulose derivatives, such as methylcellulose,hydroxyethylcellulose, or the sodium salt of carboxymethylcellulose, oracrylic polymers, such as polyacrylic acid sodium salt, or inorganicthickeners, such as bentonite. The quantity of thickening agent whenpresent can vary over a wide range, such as that of from about 0.5% to5% and preferably from about 0.5% to 3% by weight.

To illustrate the antioxidants that may be used in the present oxidationdye mixture, mention may be made of sodium sulfite, thioglycollic acid,sodium hydrosulfite and ascorbic acid. The quantity of antioxidant thatmay be contained in the instant oxidation dye mixture will usually be inthe range of from about 0.05% to 1% by weight based on the total weightof the oxidation dye mixture.

Water is ordinarily the major constituent of the present composition andcan vary over a wide range dependent in large measure on the quantity ofother additives. Thus, the water content can be as little as 20% andpreferably from about 30% to 90%.

The dyeing compositions of this invention are preferably aqueouscompositions. The term "aqueous composition" is used herein in its usualgeneric sense as embracing any water-containing composition embodied inthe invention. This includes true solutions or mixtures of the dye in anaqueous medium, either alone or in conjunction with other materials,which are also dissolved or dispersed in the aqueous medium. The dye maybe colloidally dispersed in the medium or may merely be intimately mixedtherein.

To further illustrate the various other modifiers, antioxidants,alkalizers and other adjuvants that may be incorporated in the oxidationdye mixture of this invention, reference is made to Sagarin "Cosmetics,Science and Technology" (1957), pages 505-507, Interscience Publishers,Inc., New York. The aqueous compositions of this invention may take manyforms. Thus, they may be thin or thick flowable liquids, pastes, creams,gels, etc.

To summarize the various components that may comprise the oxidation dyemixture of this invention, Table I below is given. The percentages aregiven as percent by weight based on the total weight of the oxidationdye mixture.

                  TABLE I                                                         ______________________________________                                                        % by weight                                                   Components        General    Preferred                                        ______________________________________                                        Para component    0.1 to 6   0.2 to 4                                         New meta component                                                                              0.1 to 6   0.2 to 4                                         Other oxidation dye inter-                                                    mediate           0 to 4     0.1 to 2                                         Nitro dyes        0 to 3     0.01 to 2                                        Soap              0 to 35    15 to 25                                         Surfactant        0 to 30    1 to 10                                          Thickening agent  0 to 5.0   0.05 to 3                                        Antixidants       0 to 1.0   0.05 to 1                                        Organic solvents  0 to 40    5 to 30                                          Water       QS to 100%                                                        Alkalizing agent to pH                                                                          8 to 11    9 to 10                                          ______________________________________                                    

The aforesaid oxidation dye mixtures of this invention are intended foruse in conjunction with conventional oxidation dye "developers", whichcontain the oxidizing agent necessary to effect reaction to coloredproducts. Typical developers that are useful for this purpose areaqueous solutions of hydrogen peroxide, e.g. 5 to 12%, or high viscositycreams containing in addition, for example, nonylphenol polyethyleneglycol or lauryl alcohol polyethylene glycol, in an amount of from 2-10%of the weight of developer, or crystalline peroxide such as ureaperoxide or melamine peroxide.

In use, a quantity of the developer described above is mixed with aquantity of oxidation dye composition described previously. Usually, theamount of developer taken is far in excess of that required to oxidizethe intermediates, the amounts taken being dependent on the form andconcentration of the developer selected. The mixture is well shaken andapplied to hair. It can be applied as a shampoo to the entire head,applied to one area of the hair, such as the roots and combed throughthe rest of the hair later. The mixture is allowed to remain on the headfor a period of time and is then removed by shampooing. The normal timeof application is 20-30 minutes, but application times of from 10minutes to one hour can be used.

In one form of application of the compositions of this invention, theoxidation dye mixture is dispensed from an aerosol container underpressure of a suitable propellant. The foam so obtained is mixed withthe developer, generally a solution of hydrogen peroxide, and applied tothe hair as above.

The following Examples are given to further illustrate the presentinvention. It is to be understood, however, that the invention is notlimited thereto. Unless otherwise specified, all percentages are givenas percent by weight based on the total weight of the composition.

The following expressions used in the Examples have the meaningsindicated below:

Carbopol 934 -- This is a water-soluble polymer of acrylic acid crosslinked with about 1% of a polyallyl ether of sucrose having an averagevalue of about 5.8 allyl groups for each molecule of ether and having amolecular weight in the order of magnitude of 1,000,000.

Dupanol C -- Sodium lauryl sulfate, U.S.P. grade.

EXAMPLE 1 Preparation of 2-methylamino-4-aminotoluene

15.4 g. (0.1M) of 2-amino-4-nitrotoluene was dissolved in 100 ml. 96% H₂SO₄ at room temperature with stirring and 50 ml. of a 36% solution offormaldehyde in H₂ O was added. The mixture was stirred for 30 minutesand poured on ice, neutralized with NaOH, filtered and washed. There wasobtained 16.1 g. of 2-methylamino-4-nitrotoluene; m.p. 107°-108°(Gnehm/Blume. Ann. 304, 100, gives 107.5° C). 8.3 g. of the abovecompound was reduced catalytically with Pd as catalyst and the freeamine produced was reacted with HCl to form 10 g. of the dihydrochloride(the free amine is liquid). ##STR9##

EXAMPLE 1A Dye Test of 2-methylamino-4-aminotoluene withp-phenylenediamine

0.104 g. (.0005M) 2-methylamino-4-aminotoluene dihydrochloride (metacomponent) and .054 g. (.0005M) p-phenylenediamine (para component) wasadded to 3 ml. of ethanol and 20 g. of an aqueous solution composed of1% Carbopol 934 (thickening agent) 0.1% Dupanol C (surfactant) and 3.8%ammonium acetate. The mixture was stirred with 3 ml. ammonium hydroxide(28%) and 20 ml. 6% hydrogen peroxide. A sample of human hair was dyedwith this composition for 30 minutes at 30° C. A blue color was obtainedwhich was perspiration, light and washfast, and superior in thesecharacteristics to a similar dyeing obtained in which m-toluenediaminewas used as the meta component.

EXAMPLE 1B Dye Test of 2-methylamino-4-aminotoluene usingp-toluenediamine sulfate as para component

0.109 g. (0.0005M) 2-methylamino-4-aminotoluene hydrochloride and 0.11g. (0.005M) p-toluenediamine sulfate were dissolved in 3 ml. ethanol andin a 20 cc. base made up of 1% Carbopol 934, .1% Dupanol C, 3.8%ammonium acetate and water. To this solution was added 3 ml. 28%ammonium hydroxide and 20 ml. 6% hydrogen peroxide. The resultingmixture was dyed on a sample of human hair for 30 minutes at 30° C. Thehair was dyed blue which was perspiration, light and washfast.

EXAMPLE 2 Preparation of 2-ethylamino-4-aminotoluene ##STR10## StartingMaterial

A. 15.2 g. (0.1M) 2-methyl-5-nitroaniline

B. 21.8 g. (0.2M) Ethyl bromide

C. 13.6 g. (0.1M) Sodium acetate 0.3H₂ O

D. 100 ml. Ethanol

Procedure

A, B, C and D were placed in a small autoclave and heated on a oil bathto 120°-125° C for 22 hours. The reaction mixture was cooled andfiltered and the filtrate was evaporated on a rotovac. The resultingsolid was recrystallized from EtOH--H₂ O mixture to yield 7.9 g.yellow-brown crystals (Mac Callum, Soc. 67, 247). 4.5 g. of the aboveproduct was catalytically reduced with Pd and subsequently converted tothe dihydrochloride. Weight of product = 4.36 g. The2-ethylamino-4-aminotoluene prepared by this Example was dyed out usingthe process of Examples 1A and 1B above in which the2-ethylamino-4-aminotoluene was used in place of the2-methylamino-4-aminotoluene as the meta component. These dyeingsproduced deep blue shades with good perspiration fastness.

EXAMPLE 3 Preparation of 2-propylamino-4-aminotoluene ##STR11## StartingMaterial

A. 15.2 g. (0.1M) 2-methyl-5-nitroaniline

B. 61.5 g. (0.5M) 1-bromopropane

C. 13.6 g. (0.1M) Sodium acetate 0.3H₂ O

D. 125 ml. n-propanol

Procedure

A, B, C, and D were placed in a 500 ml. 3 neck flask and heated by aheating mantle, with stirring, to reflux. The reaction was completeafter 54 hours of reflux as determined by a thin layer chromatogram. Thereaction mixture was cooled and filtered to eliminate salt. The solventwas evaporated from the filtrate on a rotary evaporator. The resultingsolid material was recrystallized from H₂ O. Orange oil insoluble in hotwater was separated by decantation.

The oil which solidifies on cooling is the product. Weight of product =7.0 g. M.P. = 54°-59° C. The product had a faint trace of impurity. 4.85g. of the above product was catalytically reduced with Pd andsubsequently converted to the dihydrochloride. Weight of productrecovered = 5.44 g. Subsequent dye tests with various para components,e.g. PPD and PTD, produced deep blue shades with good perspirationfastness. The 2-propylamino-4-aminotoluene prepared by this Example wasdyed out using the process of Examples 1A and 1B in which the2-propylamino-4-aminotoluene was used in place of the2-methylamino-4-aminotoluene as the meta component. These dyeingsproduced deep blue shades with good perspiration fastness.

EXAMPLE 4 Preparation of 2-hydroxyethylamino-4-aminotoluene ##STR12##Starting Material

A. 30.4 g. (.2M) 2-amino-4-nitrotoluene

B. 130 g. Ethanol 3A

C. Ethylene oxide (enough to complete reaction)

Procedure

A and B were mixed in a 500 ml. 3 neck flask equipped with a stirrer andreflux condenser. The reaction mixture was heated to reflux by means ofa heating mantle, and C was then slowly bubbled into the reactionmixture through a trap containing 10 ml. xylene. The ethylene oxide wasbubbled through until reaction is completed as indicated on thin layerchromatogram (total time approximately 50 hours). The resulting solutionwas evaporated of solvent on a rotary evaporator. The solid that remainswas recrystallized from deionized water. Weight of orange-red productobtained was 11.2 g. (m.p. = 89°-90° C) % N found = 14.26 Theory = 14.289 g. of the above product was catalytically reduced on a Parrhydrogenator using 5% Palladium on carbon as catalyst in an ethanolsolvent. The resulting reduced material filtered into ethanolic HCl(prepared by bubbling HCl gas into ethanol). After all the solvent isevaporated, a white solid product results. The2-hydroxyethylamino-4-aminotoluene prepared by this Example was dyed outusing the process of Examples 1A and 1B in which the2-hydroxyethylamino-4-aminotoluene was used in place of the2-methylamino-4-aminotoluene as the meta component. These dyeingsproduced deep blue shades with excellent perspiration fastness.

EXAMPLE 5 Preparation of 2-benzylamino-4-aminotoluene ##STR13## StartingMaterial

A. 15.2 g. (0.1M) 2-methyl-5-nitroaniline

B. 28.0 g. (0.2M + 10% excess) benzyl chloride

C. 13.6 g. (0.1M) Sodium acetate 0.3H₂ O

D. 100 ml. ethanol

Procedure

A, B, C and D were heated in an autoclave at 125° for 22 hours, cooledand filtered. No recrystallization was necessary. Weight of product =11.4 g. m.p. = 124°-125° C. (Ullmann, Grether, Berichte 35, 338, gives124° C). 6.05 g. of above product was reduced and converted todihydrochloride. Weight of product = 6.78 g. The2-benzylamino-4-aminotoluene prepared by this Example was dyed out usingthe process of Examples 1A and 1B above in which the2-benzylamino-4-aminotoluene was used in place of the2-methylamino-4-aminotoluene as the meta component. These dyeingsproduced blue shades.

EXAMPLE 6 Preparation of 2-methylsulfamido-4-aminotoluene ##STR14##Starting Material

A. 30.4 g. (0.2M) 2-amino-4-nitrotoluene

B. 25.2 g. (0.22M) methanesulfonyl chloride

C. 300 ml. xylene

Procedure

A and C were stirred and heated to reflux in a 1 l 3 neck flask. B wasadded dropwise. The reaction refluxed for 20 hours and the reaction wascooled and filtered. Solid material recovered was recrystallized fromethanol. The weight of product obtained = 30.0 g. m.p. = 146°-147° C.23.0 g. (.1M) of the above intermediate was reduced with Pd on catalyst.The product was recrystallized from ethanol. The weight of productobtained = 7.3 g. m.p. = 173°-173.5° C. The2-methylsulfamido-4-aminotoluene prepared by this Example was dyed outusing the process of Examples 1A and 1B above in which the2-methylsulfamido-4-aminotoluene was used in place of the2-methylamino-4-aminotoluene as the meta component. These dyeingsproduced violet blue and deep blue shades respectively withp-phenylenediamine and p-toluenediamine as para component.

EXAMPLE 7 Preparation of 2-cyanomethylamino-4-aminotoluene ##STR15##Starting Material

A. 45.6 g. (0.3M) 2-Methyl-5-nitroaniline

B. 27.0 g. Paraformaldehyde

C. 58.5 g. Potassium cyanide

D. 157.5 g. Zinc chloride

E. 1500 cc. acetic acid

Procedure

A, B, C and D were placed in a 3 l. 3 neck flask and cooled by an icebath. E with 2 ml. conc. H₂ SO₄ was added dropwise with stirring. Afterthe addition the mixture was stirred for 30 minutes and the temperaturewas then raised to 50° C over a one hour period. The reaction wasstirred at 50° C for an additional 8 hours. Contents of the flask werethen cooled and poured into 2100 ml. ice water. The resulting solid wasfiltered and washed with water. The product was recrystallized from H₂O--EtOH mixture. M.P. of yellow crystals = 148°-149° C. Analysis:

    ______________________________________                                                 Theory       Found                                                   ______________________________________                                        %C         56.54          56.12                                               H          4.71           4.86                                                N          21.98          21.40                                               ______________________________________                                    

Weight of product = 28.7 g. 6.4 g. of above product was catalyticallyreduced with Pd and subsequently converted to dihydrochloride. Weight ofproduct = 8.67 g. The cyanomethylamino-4-aminotoluene prepared by thisExample was dyed out using the process of Examples 1A and 1B above inwhich the 2-cyanomethylamino-4-aminotoluene was used in place of the2-methylamino-4-aminotoluene as the meta component. These dyeingsproduced gray-blue shades.

EXAMPLE 8

One ounce of a solution of the following composition is prepared:

    ______________________________________                                        N,N-bis(2-hydroxyethyl)-p-                                                     phenylenediamine hydrochloride                                                                             1%                                              2-Methylamino-4-aminotoluene  1%                                              oleic acid                    35%                                             ammonium hydroxide (28% Aq.)  8%                                              isopropanol                   20%                                             water                         41%                                             ______________________________________                                    

This solution is mixed with 1 oz. of 6% aqueous hydrogen peroxide andapplied to a swatch of gray hair for 20 minutes at ambient temperature.The hair is found to be dyed blue.

EXAMPLE 9

One ounce of a solution of the following composition:

    ______________________________________                                        2,6-dimethyl-p-phenylenediamine                                                                             .5%                                             N,N-bis(2,3-dihydroxypropyl)-p-                                               phenylenediamine              .1%                                             resorcinol                    .6%                                             2-propylamino-4-aminotoluene  .1%                                             4-nitro-o-phenylenediamine    .1%                                             2-nitro-p-phenylenediamine    .1%                                             hydroxyethylcellulose         1%                                              ammonium acetate              4%                                              28% aqueous ammonia           10%                                             ammonium lauryl sulfate       .1%                                             water                         92%                                             ______________________________________                                    

is mixed with 1 oz. of 6% aqueous hydrogen peroxide and applied to grayhair for 20 minutes. The hair is found to be dyed brown.

EXAMPLE 10

One ounce of a solution of the following composition:

    ______________________________________                                        N,2-dimethyl-p-phenylenediamine                                                                            3.2%                                             resorcinol                   2.1%                                             2-β-hydroxyethylamino-4-aminotoluene                                                                  .2%                                              o-phenylenediamine           .4%                                              2-nitro-p-phenylenediamine   .2%                                              Carbopol 934                 1.5%                                             ammonium acetate             5%                                               ammonia (28% aqueous)        12%                                              isopropanol                  .5%                                              sodium lauryl sulfate        .2%                                              sodium sulfite               0.7%                                             water                        83.5%                                            ______________________________________                                    

is mixed with 1 oz. of 6% aqueous H₂ O₂ containing 1% Carbopol 934 andapplied to gray hair for 20 minutes. The hair is found to be dyedchestnut.

EXAMPLE 11

One ounce of a solution of the following composition:

    ______________________________________                                        4-amino-2-methyl-N-(2-hydroxy-                                                 ethyl)-aniline hydrochloride                                                                          3.5%                                                 resorcinol               3.5%                                                 2-ethylamino-4-aminotoluene                                                                            .2%                                                  nitro-p-phenylenediamine .1%                                                  4-nitro-o-phenylenediamine                                                                             .1%                                                  oleic acid               12%                                                  ammonia                  1.5%                                                 isopropanol              7.5%                                                 sodium lauryl sulfate    .1%                                                  water                    71.5%                                                ______________________________________                                    

is mixed with 1 oz. of a solution of 1% Carbopol 934 in 6% aqueoushydrogen peroxide. The mixture is applied to gray hair for 30 minutesand produces dark brown.

EXAMPLE 12

One ounce of a solution of the following composition:

    ______________________________________                                        N,3-dimethyl-p-phenylenediamine                                                hydrochloride                1.2%                                            resorcinol                    1.3%                                            2-benzylamino-4-aminotoluene  .1%                                             nitro-p-phenylenediamine      .05%                                            oleic acid                    5%                                              diethanolamine                2%                                              isopropanol                   5%                                              glyerine                      .2%                                             water to 100%                                                                 ______________________________________                                    

was mixed with 1 oz. of 6% aqueous hydrogen peroxide containing 1%hydroxyethylcellulose. The mixture was applied to gray hair for 30minutes and then removed by shampooing. The hair was found to be dyedbrown.

EXAMPLE 13

One ounce of a solution of the following composition:

    ______________________________________                                        N-methyl-2-methoxy-p-phenylene-                                                diamine                     3.5%                                             resorcinol                   3.3%                                             2-methylsulfamido-4-aminotoluene                                                                           .1%                                              o-phenylenediamine           .5%                                              4-nitro-o-phenylenediamine   .05%                                             28% aqueous ammonia          10%                                              ammonium acetate             2.5%                                             water                        89.5%                                            ______________________________________                                    

was mixed with .5 oz. of 6% aqueous H₂ O₂ and applied to a swatch ofgray hair for 20 minutes. The dye was removed by rinsing and the hair ondrying was found to be dyed brown.

EXAMPLE 14

One ounce of a solution of the following composition:

    ______________________________________                                        p-phenylenediamine           2.5%                                             resorcinol                   2.5%                                             N,N-bis(β-hydroxyethyl)-3-methyl-                                         p-phenylenediamine sulfate  0.5%                                             2-cyanoethylamino-4-aminotoluene                                                                           .2%                                              o-phenylenediamine           .7%                                              nitro-p-phenylenediamine     .1%                                              Carbopol 934                 2%                                               28% aqueous ammonia          12%                                              sodium sulfite               1.1%                                             sodium lauryl sulfate        .2%                                              water                        88.5%                                            ______________________________________                                    

is mixed with 11/2 oz. of 4% aqueous hydrogen peroxide and applied togray hair for 30 minutes. The hair is found to be dyed dark brown.

EXAMPLE 15

An oxidation dye composition is prepared of the following ingredients,in the weight percentages given:

    ______________________________________                                        p-phenylenediamine           2.6%                                             N,N-bis-(2-hydroxyethyl)-p-                                                    phenylenediamine sulfate    0.4%                                             resorcinol                   1.0%                                             2-methylamino-4-aminotoluene 0.7%                                             4-nitro-o-phenylenediamine   0.06%                                            o-aminophenol                0.15%                                            m-aminophenol                0.3%                                             ethylenediamine tetraacetic acid                                                                           0.04%                                            isopropanol                  10%                                              ammonium hydroxide 28%       9%                                               sodium lauryl sulfate        2.5%                                             sulfonated castor oil        2.8%                                             carbitol (diethyleneglycol ethyl                                              ether)                       4%                                               oleic acid                   15%                                              propylene glycol             4%                                               water to make 100%                                                            ______________________________________                                    

Three ounces of the above composition is loaded into a co-dispensingaerosol can which employs the "OEL co-dispensing valve", as described inSanders, "Principles of Aerosol Technology", pages 348-349.

The inner compartment (peroxide bag), a flexible polyethylene bag, isfilled with the developer solution; namely, one ounce of 12% aqueoushydrogen peroxide, and the can is sealed with the introduction of 4.5 gof a propellant consisting of 35% 1,2-dichloro-1,1,2,2-tetrafluoroethaneand 65% 1,1-difluoroethane. For application to hair the contents of thecan are released as a foam consisting of an intimate mixture of theoxidation dye mixture and the developer in the ratio of 3:1. The foam isworked into the hair and is left on for twenty minutes, after which thehair is thoroughly rinsed. It is dyed dark brown.

Unless otherwise specified, all of the dyeings carried out in the aboveExamples are carried out at room temperature.

What is claimed is:
 1. Oxidation dye compositions comprising a watercontaining oxidation hair dye vehicle containing a para component andmeta component being reactive with each other in the presence of anoxidizing agent to form a colored dye on hair, said meta component beingan N² -substituted m-toluenediamine of the formula: ##STR16## ornon-toxic salts thereof, wherein R is alkyl or hydroxyalkyl; and saidpara component being selected from p-phenylenediamine, p-toluenediamine,and p-aminodiphenylamine the ph of said aqueous composition being 8-11.2. Compositions according to claim 1 wherein the alkyl or alkyl moietyof the groups represented by R contain 1 to 6 carbons and thehydroxyalkyl further contains 1 to 3 hydroxy groups.
 3. Compositionsaccording to claim 2 wherein the hair dye vehicle is an aqueous vehicle.4. Compositions according to claim 1 in which the meta componentcomprises about 0.1% to 6% by weight based on the total weight of thecomposition.
 5. Compositions according to claim 4 in which the paracomponent comprises about 0.1% to 6% by weight based on the total weightof the composition.
 6. Compositions according to claim 5 in which saidmeta component is ##STR17## or its non-toxic salts wherein alkyl has 1to 6 carbons.
 7. Compositions according to claim 6 wherein the paracomponent is p-phenylenediamine.
 8. Compositions according to claim 6wherein said para component is p-toluenediamine.
 9. Compositionsaccording to claim 6 wherein the para component is p-aminodiphenylamine.10. Compositions according to claim 5 in which said meta component is##STR18## or its non-toxic salts wherein hydroxyalkyl contains 1 to 6carbons and 1 to 3 hydroxy groups.
 11. Compositions according to claim10 wherein the para component is p-phenylenediamine.
 12. Compositionsaccording to claim 10 wherein said para component is p-toluenediamine.13. Compositions according to claim 10 wherein said para component isp-aminodiphenylamine.
 14. A method for dyeing human hair which comprisesmixing the oxidation dye composition of claim 1 with an oxidizing agent,applying the resulting mixture to human hair, and allowing said mixtureto remain in contact with said hair for a period of time to effectivelydye said hair.